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For the first time, ophiuroids have been found in South African strata predating the lowermost Bokkeveld Group. These comprise natural moulds and casts from two localities in the 'upper unit' of the Baviaanskloof Formation (Table Mountain Group). As a Pragian to earliest Emsian age has been inferred for this member, the new taxa comprise the earliest high-palaeolatitude ophiuroid records from southern Gondwana. Morphological analysis of the specimens revealed the presence of two distinct taxa. One is here described as Krommaster spinosus gen. et sp. nov., a new encrinasterid characterised by very large spines on the dorsal side of the disc, the ventral interradial marginal plates and the arm midlines. The second taxon is a poorly preserved specimen of Hexuraster weitzi, a cheiropterasterid previously described from the slightly younger Bokkeveld Group., Competing Interests: The authors have declared that no competing interests exist., (Copyright: © 2023 Reddy et al. This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.)

This study presents multiple sulphur isotope ( 32 S, 33 S, 34 S, 36 S) data on pyrites from silicified volcano-sedimentary rocks of the Paleoarchean Onverwacht Group of the Barberton greenstone belt, South Africa. These rocks include seafloor cherts and felsic conglomerates that were deposited in shallow marine environments preserving a record of atmospheric and biogeochemical conditions on the early Earth. A strong variation in mass independent sulphur isotope fractionation (MIF-S) anomalies is found in the cherts, with Δ 33 S ranging between -0.26‰ and 3.42‰. We explore possible depositional and preservational factors that could explain some of this variation seen in MIF-S. Evidence for microbial activity is recorded by the c. 3.45 Ga Hooggenoeg Formation Chert (HC4) preserving a contribution of microbial sulphate reduction (-Δ 33 S and -δ 34 S), and a c. 3.33 Ga Kromberg Formation Chert (KC5) recording a possible contribution of microbial elemental sulphur disproportionation (+Δ 33 S and -δ 34 S). Pyrites from a rhyo-dacitic conglomerate of the Noisy Formation do not plot along a previously proposed global Felsic Volcanic Array, and this excludes short-lived pulses of intense felsic volcanic gas emissions as the dominant control on Archean MIF-S. Rather, we suggest that the MIF-S signals measured reflect dilution during marine deposition, early diagenetic modification, and mixing with volcanic/hydrothermal S sources. Given the expanded stratigraphic interval (3.47-3.22 Ga) now sampled from across the Barberton Supergroup, we conclude that large MIF-S exceeding >4‰ is atypical of Paleoarchean near-surface environments on the Kaapvaal Craton., (© 2022 John Wiley & Sons Ltd.)

The Waterloo Farm lagerstätte in South Africa provides a uniquely well-preserved record of a Latest Devonian estuarine ecosystem. Ecological evidence from it is reviewed, contextualised, and compared with that available from the analogous Swartvlei estuarine lake, with a particular emphasis on their piscean inhabitants. Although the taxonomic affinities of the estuarine species are temporally very different, the overall patterns of utilisation prove to be remarkably congruent, with similar trophic structures. Significantly, both systems show evidence of widespread use of estuaries as fish nurseries by both resident and marine migrant taxa. Holocene estuaries are almost exclusively utilised by actinopterygians which are overwhelmingly dominated by oviparous species. Complex strategies are utilised by estuarine resident species to avoid exposure of eggs to environmental stresses that characterize these systems. By contrast, many of the groups utilising Devonian estuaries were likely live bearers, potentially allowing them to avoid the challenges faced by oviparous taxa. This may have contributed to dominance of these systems by non-actinoptergians prior to the End Devonian Mass Extinction. The association of early aquatic tetrapods at Waterloo Farm with a fish nursery environment is consistent with findings from North America, Belgium and Russia, and may be implied by the estuarine settings of a number of other Devonian tetrapods. Tetrapods apparently replace their sister group, the elpistostegids, in estuaries with both groups having been postulated to be adaptated to shallow water habitats where they could access small piscean prey. Correlation of tetrapods (and elpistostegids) with fish nursery areas in the Late Devonian lends strong support to this hypothesis, suggesting that adaptations permitting improved access to the abundant juvenile fish within the littoral zone of estuarine lakes and continental water bodies may have been pivotal in the evolution of tetrapods., (© 2020 Cambridge Philosophical Society.)

Atmospheric oxygen levels control the oxidative side of key biogeochemical cycles and place limits on the development of high-energy metabolisms. Understanding Earth's oxygenation is thus critical to developing a clearer picture of Earth's long-term evolution. However, there is currently vigorous debate about even basic aspects of the timing and pattern of the rise of oxygen. Chemical weathering in the terrestrial environment occurs in contact with the atmosphere, making paleosols potentially ideal archives to track the history of atmospheric O 2 levels. Here we present stable chromium isotope data from multiple paleosols that offer snapshots of Earth surface conditions over the last three billion years. The results indicate a secular shift in the oxidative capacity of Earth's surface in the Neoproterozoic and suggest low atmospheric oxygen levels (<1% PAL pO 2 ) through the majority of Earth's history. The paleosol record also shows that localized Cr oxidation may have begun as early as the Archean, but efficient, modern-like transport of hexavalent Cr under an O 2 -rich atmosphere did not become common until the Neoproterozoic., (© 2019 John Wiley & Sons Ltd.)

The mineral sturmanite is a hydrated calcium iron aluminium manganese sulphate tetrahydroxoborate hydroxide of formula Ca6(Fe, Al, Mn)2(SO4)2(B(OH)4)(OH)12·26H2O. We have studied the mineral sturmanite using a number of techniques, including SEM with EPMA and vibrational spectroscopy. Chemical analysis shows a homogeneous phase, composed by Ca, Fe, Mn, S, Al and Si. B is not determined in this EPMA technique. An intense Raman band at 990cm(-1) is assigned to the SO4(2-) symmetric stretching mode. Raman spectroscopy identifies multiple sulphate symmetric stretching modes in line with the three sulphate crystallographically different sites. Raman spectroscopy also identifies a band at 1069cm(-1) which may be attributed to a carbonate symmetric stretching mode, indicating the presence of thaumasite. Infrared spectra display two bands at 1080 and 1107cm(-1) assigned to the SO4(2-) antisymmetric stretching modes. The observation of multiple bands in this ν4 spectral region offers evidence for the reduction in symmetry of the sulphate anion from Td to C2v or even lower symmetry. The Raman band at 3622cm(-1) is assigned to the OH unit stretching vibration and the broad feature at around 3479cm(-1) to water stretching bands. Infrared spectroscopy shows a set of broad overlapping bands in the OH stretching region. Vibrational spectroscopy enables an assessment of the molecular structure of sturmanite to be made., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Gaudefroyite Ca4MN3+3-x (BO3)3(CO3) (O, OH)3 is an unusual mineral containing both borate and carbonate groups and is found in the oxidation zones of manganese minerals, and it is black in color. Vibrational spectroscopy has been used to explore the molecular structure of gaudefroyite. Gaudefroyite crystals are short dipyramidal or prismatic with prominent pyramidal terminations, to 5 cm. Two very sharp Raman bands at 927 and 1076 cm(-1) are assigned to trigonal borate and carbonate respectively. Broad Raman bands at 1194, 1219 and 1281 cm(-1) are attributed to BOH in-plane bending modes. Raman bands at 649 and 670 cm(-1) are assigned to the bending modes of trigonal and tetrahedral boron. Infrared spectroscopy supports these band assignments. Raman bands in the OH stretching region are of a low intensity. The combination of Raman and infrared spectroscopy enables the assessment of the molecular structure of gaudefroyite to be made., (Copyright © 2013 Elsevier B.V. All rights reserved.)